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4 Priciptation
4 Priciptation
1
Precipitation titration
Introduction
Two or more soluble species combine to form an insoluble product
that we call a precipitate Or the formation of a slightly soluble
solid from solution (the reverse of dissolution).
A reaction in which the analyte and titrant form an insoluble
precipitate also can serve as the basis for a titration.
This type of titration is a precipitation titration.
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Introduction
Analyt Titran
e Produc
t 5
Limitation of precipitation titration
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Solubility product
The factor governing the completness of a precipitation rxn
is the solubility of the ppt formed:
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Precipitation titration…
Solubility product
o A saturated solution of a slightly soluble salt in contact
with an undissolved salt involves equilibrium like the
one below:
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cont...
Calculation of solubility product from solubility
If the solubility of AgCl is 0.0015g/L
[AgCl] = 0.0015/143.3 = 1.05x 10-5 M
AgCl
↔
Ag+ + Cl- SAgCl =
[Ag+] + [Cl-]
= 1.05x 10-5 x
1.05x 10-5
= 1.1 x 10-10
Ag2S ↔ 2Ag+ + S2- 6x10-50 = 4X3
Calculation of
X 2X X X3 = 1.5 x 10-50
solubility from
S Ag2S = [Agproduct
solubility +]2 [S2-] = 6x10- X = 2.47 x 10-17 M
50
Q. The solubility of calcium sulphate (CaSO4) is found to be 0.67 g/L. Calculate the
value of Ksp for calcium sulphate.
- No of mole of CaSO4
- For every mole of CaSO4 that dissolves, 1 mole of Ca2+ and 1 mole of SO4 are
2-
- Hence:
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Precipitation titration…
precipitation Calculations
If we have a given set of concentration conditions we can
calculate a solubility quotient, Q c , and compare it to the
Ksp
The solubility quotient (often called the ion product)
has the same form as the solubility constant expression,
but the concentrations of the substances are not
necessarily equilibrium values
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Precipitation titration…
1. Temperature effect
Most of inorganic salts increase its solubility by
increasing temperature.
Exception-Hg 2 Cl 2 , MgNH 4 PO 4
2. Solvent effect
Most of inorganic salts dissolve in water but not
in organic solvent.
In order to form a precipitate,
the product formed should be insoluble in
the solvent.
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Precipitation titration…
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Argentiometric titration
1. Mohr method
Potassium chromate is Used as indicator in the titration of chloride
ions with standard silver nitrate in neutral solution
It gives a precipitate of red silver Chromate at the end point
Cont.…
But this precipitate has a greater solubility than that of AgCl
Therefore, AgCl is formed first and after all Cl- is consumed, the
first drop of Ag+ in excess will react with the chromate indicator
giving a reddish precipitate.
Adsorbed ions of the sample become trapped & cause low results
Exercise 1
A 0.32 g sample containing KCl ( mw = 74.6 ) is dissolved in 50 mL of water
and titrated to the Ag2CrO4 end point, requiring 16.9 mL of 0.1 M AgNO3. A
blank titration requires 0.7 mL of titrant to reach the same end point. Report
the %w/w KCl in the sample ?
Answer
Application:
2. Potassium iodide
KI can be determined by direct titration with AgNO3 using iodine & starch
as indictor.
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Cont.….
When excess of std. AgNO3 so/n is added in to so/n of
halide
preparation of silver halide occurs:-
– Ag+ (excess) + X- (analyte) ↔ AgX (ppt) + excess Ag+
Answer:
Application
Sodium chloride:-
Chlorbutol:-
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Reading assignment
1. Fajans Method
2. Mercuremetric method